N-substituted-N&#39;,N&#39;-disubstituted glycinamide fungicides

ABSTRACT

The N-substituted-N&#39;,N&#39;-disubstituted α-aminoacetamides of this invention are effective fungicides. In particular, they possess good activity against Bean Powdery Mildew.

This is a division of application Ser. No. 446,802, filed Dec. 3, 1982,now U.S. Pat. No. 4,532,251.

BACKGROUND OF THE INVENTION

This invention is drawn to novel fungicides. With the world moredependent for food on an ever decreasing amount of cultivated farmland,it is increasingly important to develop effective fungicides whichprotect crops from fungicidal destruction.

Kozlik et al, in CA 79:53327Z, disclosed 1-carbamoylimidazoles asinsecticidal.

Brookes et al, in U.S. Pat. Nos. 4,080,462 and 3,991,071, disclosed1-(N,N-disubstituted carbamoyl and thiocarbamoyl)-imidazoles asfungicidal.

Birchmore et al, in U.S. Pat. No. 4,250,179, disclosed complexes of ametal salt with N,N-disubstituted carbamoyl imidazoles (including someof those disclosed by Brookes et al) as fungicidal.

SUMMARY OF THE INVENTION

The compounds of the present invention are represented by the formula:##STR1##

wherein R is phenyl, or phenyl substituted with 1 to 4 substituentsindependently selected from fluoro, chloro, bromo, iodo, nitro, loweralkyl, or trihalomethyl; R¹ is lower alkyl; R² is a 5- or 6-memberheterocyclic ring containing 1 to 2 nitrogen atoms and the remainder ofthe ring atoms carbon atoms, with the proviso that a nitrogen of the 5-or 6-member heterocyclic ring is not bonded to the ##STR2## group; andR³, R⁴ and R⁵ are independently lower alkyl, or hydrogen.

Among other factors, the present invention is based on my finding thatthe compounds of this invention are effective fungicides. In particular,they possess good activity against Bean Powdery Mildew.

In part due to their superior fungicidal activity, preferred R groupsinclude the trihalophenyl and dihalophenyl groups. Particularlypreferred R groups are 2,4,6-trihalophenyl and 2,6-dihalophenyl.

Preferred halogens are chloro and bromo.

Preferred R¹ lower alkyl groups are n-propyl and ethyl.

Preferred R² groups include, for instance, 3-pyridyl, 5-pyrimidyl,3-pyrazinyl, and 5-(1-methylimidazolyl).

Particularly preferred R² groups are the 6-member heterocyclescontaining 1 to 2 nitrogen atoms and include, for instance, 3-pyridyl,5-pyrimidyl, 3-pyrazinyl, and the like.

Most preferably, R² is 3-pyridyl.

Preferably, R³, R⁴ and R⁵ are hydrogen.

Definitions

As used herein, the following terms have the following meanings, unlessexpressly stated to the contrary.

The term "alkyl" refers to both straight- and branched-chain alkylgroups. Generally, such alkyl groups contain from 1 through 12 carbonatoms.

The term "lower alkyl" refers to both straight- and branched-chain alkylgroups having a total from 1 through 6 carbon atoms and includesprimary, secondary and tertiary alkyl groups. Typical lower alkylsinclude, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl,t-butyl, n-hexyl, and the like.

The term "halo" or "halogen atom" refers to the groups fluoro, chloro,bromo and iodo.

The term "a 6-member heterocyclic ring containing 1 to 2 nitrogen atoms"refers to the groups pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, and thelike.

The term "a 5-member heterocyclic ring containing 1 to 2 nitrogen atoms"refers to the groups imidazolyl, pyrrolyl, pyrazolyl, and the like.

The term "glycinamide" refers to the group: ##STR3## with the nitrogenof the amino group referred to as the N'- group and the nitrogen of theamide referred to as the N- group. Thus, the term"N-(2,4,6-trichlorophenyl), N'-(n-propyl) glycinamide" refers to thegroup: ##STR4##

The term "N-(2,4,6-trichlorophenyl), N'-(n-propyl)N'-(3-pyridylcarbonyl)-α,α-dimethylglycinamide" refers to the group:##STR5##

DETAILED DESCRIPTION OF THE INVENTION

The compounds of the present invention are conveniently preparedaccording to the following synthetic scheme: ##STR6##

wherein R, R¹, R², R³, R⁴, and R⁵ are as above defined; X and X' areindependently halogen; and b is a base.

Reaction (1) is conducted by adding an essentially equimolar amount ofan α-haloacetyl halide, III, to II. The reaction is conducted in theliquid phase employing an aprotic anhydrous organic solvent such aschloroform, methylene chloride, toluene, and the like. An essentiallyequimolar amount of a base, IV, is added to the system to scavenge theacid generated during the reaction. Preferably, an organic base such astrialkylamine (e.g., triethylamine), pyridine, and the like, isemployed. Reaction pressure is not critical and for convenience, isconducted at atmospheric pressure. The reaction is generally conductedat from -20° C. to 80° C., although preferably at from 0° C. to 25° C.,and is generally complete from within 1 to 24 hours. The resultingamide, V, is then isolated by conventional procedures such asextraction, filtration, chromatography, distillation, or alternatively,is used in Reaction (2) without purification and/or isolation.

Reaction (2) is conducted by adding an essentially equimolar amount ofthe appropriate primary amine, VI, to V. An essentially equimolar amountof a base, IV, is added to the system in order to scavenge the acidgenerated during the reaction. Preferably, an organic base such astrialkylamine (e.g., triethylamine), pyridine, and the like, isemployed. The reaction is done in the liquid phase using an inertanhydrous organic solvent such as chloroform, methylene chloride,dimethoxyethane, and the like. Alternatively, in lieu of adding solventand base, the reaction may be accomplished by using an excess amount ofthe primary amine, VI. Reaction pressure is not critical and forconvenience, the reaction is generally conducted at atmosphericpressure. The reaction is generally conducted at from 0° C. to 100° C.,although preferably at from 20° C. to 50° C., and is generally completefrom within 1 to 24 hours. The product, VII, is isolated by conventionalprocedures such as extraction, filtration, chromatography, distillation,or alternatively, is used in Reaction (3) without purification and/orisolation.

Reaction (3) is conducted by first preparing reagent VIII. VIII isprepared by adding an essentially equimolar amount ofcarbonyldiimidazole to the appropriate acid, R² CO₂ H wherein R² is asdefined above. The reaction is conducted in the liquid phase using aninert anhydrous organic solvent such as chloroform, methylene chloride,dimethoxyethane, toluene, and the like. Reaction pressure is notcritical and for convenience, the reaction is generally conducted atatmospheric pressure. The reaction is generally conducted at from 0° C.to 100° C., although preferably at room temperature, and is generallycomplete from within 1 to 24 hours. The resulting carboxylic acidimidazolide, VIII, may be isolated by conventional procedures such asextraction, filtration, chromatography, distillation, and the like.Alternatively and preferably, the reagent is not isolated from thereaction solution but an essentially equimolar amount of the amine, VII,is added to the system. Reaction pressure is not critical and forconvenience, this reaction is generally conducted at atmosphericpressure. After addition of VII, the reaction is generally conducted atroom temperature and is generally complete from within 1 to 24 hours.The product, I, is then isolated by conventional procedures such asextraction, filtration, chromatography, distillation, and the like.

Utility

The compounds of this invention are useful for controlling fungi,particularly leaf blights caused by Septoria apii and Alternaria solaniconidia, and powdery mildew caused by Erysiphe polygoni.

However, some fungicidal compounds of the invention may be morefungicidally active than others against particular fungi.

When used as fungicides, the compounds of the invention are applied infungicidally effective amounts to fungi and/or their habitats, such asvegetative hosts and non-vegetative hosts, e.g., animal products. Theamount used will, of course, depend on several factors such as the host,the type of fungus, and the particular compound of the invention. Aswith most pesticidal compounds, the fungicides of the invention are notusually applied full strength, but are generally incorporated withconventional, biologically inert extenders or carriers normally employedfor facilitating dispersion of active fungicidal compounds, recognizingthat the formulation and mode of application may affect the activity ofthe fungicide. Thus, the fungicides of the invention may be formulatedand applied as granules, as powdery dusts, as wettable powders, asemulsifiable concentrates, as solutions, or as any of several otherknown types of formulations, depending on the desired mode ofapplication.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersants. These compositionsnormally contain from about 5% to 80% fungicide, and the rest inertmaterial, which includes dispersing agents, emulsifying agents andwetting agents. The powder may be applied to the soil as a dry dust, orpreferably as a suspension in water. Typical carriers include fuller'searth, kaolin clays, silicas, and other highly absorbent, readilywettable, inorganic diluents. Typical wetting, dispersing or emulsifyingagents include, for example: the aryl and alkylaryl sulfonates and theirsodium salts; alkylamide sulfonates, including fatty methyl taurides;alkylaryl polyether alcohols, sulfated higher alcohols and polyvinylalcohols; polyethylene oxides; sulfonated animal and vegetable oils;sulfonated petroleum oils; fatty acid esters of polyhydric alcohols andthe ethylene oxide addition products of such esters; and the additionproducts of long-chain mercaptans and ethylene oxide. Many other typesof useful surface-active agents are available in commerce. Thesurface-active agent, when used, normally comprises from 1% to 15% byweight of the fungicidal composition.

Dusts are freely flowing admixtures of the active fungicide with finelydivided solids such as talc, natural clays, kieselguhr, pyrophyllite,chalk, diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, lime, flours, and other organic and inorganic solidswhich act as dispersants and carriers for the toxicant. These finelydivided solids have an average particle size of less than about 50microns. A typical dust formulation useful herein contains 75% silicaand 25% of toxicant.

Useful liquid concentrates include the emulsifiable concentrates, whichare homogeneous liquid or paste compositions which are readily dispersedin water or other dispersant, and may consist entirely of the fungicidewith a liquid or solid emulsifying agent, or may also contain a liquidcarrier such as xylene, heavy aromatic naphthas, isophorone, and othernonvolatile organic solvents. For application, these concentrates aredispersed in water or other liquid carrier, and are normally applied asa spray to the area to be treated.

Other useful formulations for fungicidal applications include simplesolutions of the active fungicide in a dispersant in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene, or other organic solvents. Granularformulations, wherein the fungicide is carried on relatively coarseparticles, are of particular utility for aerial distribution or forpenetration of cover-crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low-boiling dispersant solvent carrier, suchas the Freons, may also be used. All of those techniques for formulatingand applying fungicides are well known in the art.

The percentages by weight of the fungicide may vary according to themanner in which the composition is to be applied and the particular typeof formulation, but in general comprise 0.5% to 95% of the toxicant byweight of the fungicidal composition.

The fungicidal compositions may be formulated and applied with otheractive ingredients, including other fungicides, insecticides,nematocides, bactericides, plant-growth regulators, fertilizers, etc.

A further understanding of the invention can be had in the followingnon-limiting Examples. Wherein, unless expressly stated to the contrary,all temperatures and temperature ranges refer to the Centigrade systemand the term "ambient" or "room temperature" refers to about 20° C. to25° C. The term "percent" refers to weight percent and the term "mole"or "moles" refers to gram moles. The term "equivalent" refers to areagent equal in moles to the moles of the preceding or succeedingreagent recited in that example in terms of finite moles or finiteweight or volume. Also, unless expressly stated to the contrary,geometric isomer and racemic mixtures are used as starting materials andcorrespondingly, isomer mixtures are obtained as products.

EXAMPLES Example 1 Preparation of α-bromo-N-(2,4,6-trichlorophenyl)acetamide

2,4,6-trichloroaniline, 49.1 gm, was added to 250 ml of methylenechloride. The system was cooled to 0° C. and 34.8 ml of triethylaminewas then added. After addition of the triethylamine, 21.8 ml ofbromoacetylbromide was added. The system was allowed to warm to roomtemperature and stirred there for 18 hours. The reaction was thenstopped and the solvent was washed with saturated sodium bicarbonatesolution. The methylene chloride layer was separated and partiallystripped when a solid precipitated from solution. The solid was filteredand air dried to yield 41.4 gm of α-bromo-(2,4,6-trichlorophenyl)acetamide as a gray solid.

Similarly, by following the procedure outlined above and using theappropriate starting material and reagents, the following are prepared:

α-chloro-α,α-dimethyl-N-(2,4,6-trichlorophenyl) acetamide;

α-bromo-N-(2,6-dichlorophenyl) acetamide;

α-chloro-N-(4-t-butylphenyl) acetamide;

α-chloro-N-(2,4,6-tribromophenyl) acetamide;

α-bromo-N-(2,6-dibromophenyl) acetamide;

α-bromo-N-[3,5-di-(trifluoromethyl)phenyl]acetamide;

α-bromo-N-methyl-N-(2,4,6-trichlorophenyl) acetamide; and

α-bromo-N-(2,4,6-trimethylphenyl) acetamide.

Example 2 Preparation of N-(2,4,6-trichlorophenyl)-N'-(n-propyl)glycinamide

α-bromo-N-(2,4,6-trichlorophenyl) acetamide, 41.4 gm, was added to 100ml of n-propylamine. The system was heated at reflux for 16 hours. Thereaction was then stopped and the excess n-propylamine was removed bystripping. The residue was dissolved in methylene chloride. Themethylene chloride solution was washed with water. The remainingunreacted α-bromo-N-(2,4,6-trichlorophenyl) acetamide precipitated fromsolution and was then filtered. The methylene chloride was removed bystripping to give 15.1 gm of N-(2,4,6-trichlorophenyl)-N'-(n-propyl)glycinamide.

Similarly, by following the procedure outlined in the above example andusing the appropriate starting material and reagents, the following areprepared:

N-(2,4,6-tribromophenyl)-N'-(n-propyl) glycinamide;

N-(2,4,6-tribromophenyl)-N'-ethyl glycinamide;

N-(2,6-dichlorophenyl)-N'-ethyl glycinamide;

N-(4-t-butylphenyl)-N'-(n-propyl) glycinamide;

N-(2,4,6-trimethylphenyl)-N'-(n-propyl) glycinamide;

N-(4,6-dichlorophenyl)-N'-ethyl glycinamide; and

N-(4-nitrophenyl)-N'-ethyl glycinamide.

Example 3 Preparation of N-(2,4,6-trichlorophenyl), N'-(n-propyl),N'-(3-pyridylcarbonyl) glycinamide

(a) 3-pyridine carboxylic acid, 2.5 gm, was added to 40 ml of methylenechloride. 3.2 gm of carbonyldiimidazole was added to the system. Thesystem was stirred at room temperature for 18 hours to give the3-pyridyl carboxylic acid imidazolide.

(b) N-(2,4,6-trichlorophenyl)-N'-(n-propyl) glycinamide, 5.9 gm, wasthen added to 3-pyridyl carboxylic acid imidazolide mixture of Step (a).The system was stirred at room temperature for 24 hours. The reactionwas then stopped and the methylene chloride solution was washed withsodium bicarbonate solution and then with water. The methylene chloridesolution was dried over magnesium sulfate and the methylene chlorideremoved by stripping to give 2.3 gm of the N-(2,4,6-trichlorophenyl),N'-(n-propyl), N'-(3-pyridylcarbonyl) glycinamide.

Similarly, by following the procedure outlined in the above example andusing the appropriate starting material and reagents, the following areprepared:

N-(2,4,6-tribromophenyl)-N'-(n-propyl), N'-(5-pyrimidylcarbonyl)glycinamide;

N-(2,6-dibromophenyl)-N'-ethyl, N'-pyrazinylcarbonyl glycinamide;

N-(2,6-dichlorophenyl)-N'-ethyl, N'-(1-methyl-5-imidazolylcarbonyl)glycinamide;

N-(4-t-butylphenyl)-N'-(n-propyl), N'-(5-pyrimidylcarbonyl) glycinamide;and

N-(2,6-dimethylphenyl)-N'-(n-propyl), N'-(3-pyridylcarbonyl)glycinamide.

Compounds made according to Examples 1 to 3 are shown in Table I.

Example A Bean Powdery Mildew

The compounds of the invention were tested for the control of the BeanPowdery Mildew organism Erysiphe polygoni. Seedling bean plants weresprayed with a 250-ppm solution of the test compound in acetone, waterand a nonionic emulsifier. The sprayed plants were then inoculated 1 daylater with the organism. The plants were maintained for 10 days attemperatures of 68° F. at night with daytime temperatures of 72° F. to80° F.; relative humidity was maintained at 40% to 60%. The percentdisease control provided by a given test compound was based on thepercent disease reduction relative to the untreated check plants. Theresults are tabulated in Table II.

Example B Tomato Late Blight

Compounds of the invention were tested for the preventative control ofthe Tomato Late Blight organism Phytophthora infestans. Five- tosix-week-old tomato (cultivar Bonny Best) seedlings were used. Thetomato plants were sprayed with a 250-ppm suspension of the testcompound in acetone, water and a nonionic emulsifier. The sprayed plantswere then inoculated 1 day later with the organism, placed in anenvironmental chamber and incubated at 66° F. to 68° F. and 100%relative humidity for at least 16 hours. Following the incubation, theplants were maintained in a greenhouse for approximately 7 days. Thepercent disease control provided by a given test compound was based onthe percent disease reduction relative to untreated check plants. Theresults are tabulated in Table II.

Example C Celery Late Blight

The Celery Late Blight tests were conducted using celery (Utah) plants11 weeks old. The Celery Late Blight organism was Septoria apii. Thecelery plants were sprayed with 250-ppm solutions of the candidatetoxicant mixed with acetone, water and a nonionic emulsifier. The plantswere then inoculated with the organism and placed in an environmentalchamber and incubated at 66° F. to 68° F. in 100% relative humidity foran extended period of time (approximately 48 hours). Following theincubation, the plants were allowed to dry and then were maintained in agreenhouse for approximately 14 days. The percent disease controlprovided by a given candidate toxicant is based on the percent diseasereduction relative to untreated check plants. The results are reportedin Table II.

Example D Tomato Early Blight

Compounds of the invention were tested for the control of the TomatoEarly Blight organism Alternaria solani conidia. Tomato (variety BonnyBest) seedlings of 6- to 7-weeks old were used. The tomato plants weresprayed with a 250-ppm solution of the test compound in anacetone-and-water solution containing a small amount of a nonionicemulsifier. The sprayed plants were inoculated 1 day later with theorganism, placed in the environmental chamber and incubated at 66° F. to68° F. and 100% relative humidity for 24 hours. Following theincubation, the plants were maintained in a greenhouse for about 12days. Percent disease control was based on the percent diseasedevelopment on untreated check plants. The compounds tested and theresults are tabulated in Table II.

Example E Grape Downy Mildew

The compounds of the invention were tested for the control of the GrapeDowny Mildew organism Plasmopara viticola. Detached leaves, between 70mm and 85 mm in diameter, 7-week-old Vitis vinifera cultivar Emperorgrape seedlings were used as hosts. The leaves were sprayed with a250-ppm solution of the test compound in acetone. The sprayed leaveswere dried, inoculated with a spore suspension of the organism, placedin a humid environmental chamber and incubated at 66° F. to 68° F. andabout 100% relative humidity. After incubation for 2 days, the plantswere then held in a greenhouse 7 to 9 days; then the amount of diseasecontrol was determined. The percent disease control provided by a giventest compound was based on the percent disease reduction relative tountreated check plants. The results are tabulated in Table II.

Example F Leaf Rust

The Leaf Rust test was made using pinto beans. The pathogen was Uromycesphaseoli tipica. The pinto bean plants were sprayed with a 250-ppmsolution of the test compound in an acetone-water mixture containing anonionic emulsifier. The treated plants were inoculated thereafter withthe pathogen and then incubated in an environmental chamber forapproximately 20 hours at 100% relative humidity and a temperature of68° F. to 70° F. The plants were then removed from the chamber, allowedto dry, and then maintained in a greenhouse at a 60% to 80% relativehumidity. The rate of infection on the leaves was made after about 14days. The percent disease control provided by a given test compound wasbased on the percent disease reduction relative to untreated checkplants. The results are reported in Table II.

Example G Rice Blast

Compounds of this invention were tested for control of the Rice Blastorganism Piricularia oryzae, using 10- to 14-day-old rice plantseedlings (Calrose M-9 variety). Seedling plants were sprayed with a625-ppm solution of the test compound in acetone, water and a nonionicemulsifier (ORTHO X-77 spreader). The sprayed plants were inoculated 1day later with the organism in an environmental chamber. Afterinoculation, the plants were kept in an environmental chamber for about48 hours under conditions of about 72° F. to 75° F. and about 100%relative humidity. Following the incubation period, the plants wereplaced in a greenhouse with a temperature of about 72° F. and maintainedwith bottom watering for about 12 to 16 days. The percent diseasecontrol provided by a given test compound is based on a comparison ofthe percentage disease relative to the percent disease development onthe untreated check plants: ##EQU1## The results are tabulated in TableII.

                                      TABLE I                                     __________________________________________________________________________                                    ANALYSIS                                      Compound                        Carbon Hydrogen                                                                             Nitrogen                        No.   Compound                  Calc.                                                                            Found                                                                             Calc.                                                                            Found                                                                             Calc.                                                                            Found                                                                             Form                     __________________________________________________________________________           ##STR7##                 51.02                                                                            49.30                                                                             4.03                                                                             3.79                                                                              10.50                                                                             9.75                                                                             oil                      2                                                                                    ##STR8##                 70.12                                                                            68.68                                                                             7.13                                                                             7.57                                                                              12.91                                                                            13.22                                                                             oil                      __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                        Fungicidal Activity % Control                                                 Compound No.                                                                            GDM     TLB    CLB   TEB  BR   BPM  RB                              ______________________________________                                        1         3        0     50    85   4    100  0                               2         7       10     58    22   0     53  0                               ______________________________________                                         GDM -- Grape Downy Mildew (Plasmopara viticola)                               TLB -- Tomato Late Blight (Phytophthora infestans conidia)                    CLB -- Celery Late Blight (Septoria apii)                                     TEB -- Tomato Early Blight (Alternaria solani conidia)                        BR -- Bean Rust Eradicant (Uromyces phaseoli tipica)                          BPM -- Bean Powdery Mildew (Erysiphe polygoni)                                RB -- Rice Blast (Piricularia oryzae)                                    

What is claimed is:
 1. A compound of the formula: ##STR9## wherein R isphenyl, or phenyl substituted with 1 to 4 substituents independentlyselected from fluoro, chloro, bromo, iodo, nitro, lower alkyl ortrihalomethyl; R¹ is lower alkyl; R² is a 6-member aromatic heterocyclicring containing two ring nitrogens and the remainder of the ring atomscarbon atoms, with the proviso that a nitrogen of the 6-memberheterocyclic ring is not bonded to the ##STR10## group; and R³, R⁴ andR⁵ are independently lower alkyl or hydrogen.
 2. A compound of theformula defined in claim 1 wherein R is 2,4,6-trihalophenyl.
 3. Acompound of the formula defined in claim 2 wherein R is2,4,6-trichlorophenyl.
 4. A compound of the formula defined in claim 1wherein R² is pyrazinyl, pyrimidyl.
 5. A compound of the formula definedin claim 4 wherein R is trihalophenyl or 2,6-di-(lower alkyl).
 6. Acompound of the formula defined in claim 5 wherein R¹ is n-propyl.
 7. Acompound of the formula defined in claim 6 wherein R is2,4,6-trichlorophenyl.
 8. A compound of the formula defined in claim 7wherein R³, R⁴ and R⁵ are hydrogen.
 9. A compound of the formula definedin claim 8 wherein R² is pyrazinyl.
 10. A compound of the formuladefined in claim 8 wherein R² is pyrimidyl.
 11. A compound of theformula defined in claim 8 wherein R² is 5-pyrimidyl.
 12. A fungicidalcomposition comprising a biologically inert carrier and a fungicidallyeffective amount of a compound of the formula defined in claim
 1. 13. Afungicidal composition comprising a biologically inert carrier and afungicidally effective amount of a compound of the formula defined inclaim
 4. 14. A fungicidal composition comprising a biologically inertcarrier and a fungicidally effective amount of a compound of the formuladefined in claim
 9. 15. A fungicidal composition comprising abiologically inert carrier and a fungicidally effective amount of acompound of the formula defined in claim
 10. 16. A fungicidalcomposition comprising a biologically inert carrier and a fungicidallyeffective amount of a compound of the formula defined in claim
 11. 17. Amethod for controlling fungi which comprises contacting said fungi ortheir growth enviornment with a fungicidally effective amount of acompound of the formula defined in claim
 1. 18. A method for controllingfungi which comprises contacting said fungi or their growth enviornmentwith a fungicidally effective amount of a compound of the formuladefined in claim
 4. 19. A method for controlling fungi which comprisescontacting said fungi or their growth enviornment with a fungicidallyeffective amount of a compound of the formula defined in claim
 9. 20. Amethod for controlling fungi which comprises contacting said fungi ortheir growth enviornment with a fungicidally effective amount of theformula defined in claim
 10. 21. A method for controlling fungi whichcomprises contacting said fungi or their growth environment with afungicidally effective amount of the formula defined in claim 11.